Hexahydrotriazine, dithiazine, and thioether functionalized materials

Abstract

Synthetic schemes for preparation of polymers and polymer precursors having various functional groups is provided. These synthetic schemes are used to prepare polymeric, oligomeric, or monomeric materials incorporating 1,3,5-hexahydrotriazine moieties. These hexandortriazine moieties can be further reacted to form dithiazine and thioether moieties. In certain synthetic schemes, 1,3,5-hexahydrotriazine moieties are incorporated as crosslinker groups for providing crosslinked polymeric materials. Crosslinker groups formed with these triazine moieties provide chemically reversible crosslinks, which allow such otherwise intractable crosslinked polymeric materials to be recycled and/or reprocessed by removal/reversal of crosslinks.

What is claimed is: 
     
       1. A method, comprising:
 exposing a first monomer including a primary amine functional group to paraformaldehyde and a first primary amine compound and forming a second monomer including a 1,3,5-hexahydrotriazine group; and 
 polymerizing the second monomer and forming a first polymer including the 1,3,5-hexahydrotriazine group. 
 
     
     
       2. The method of  claim 1 , further comprising:
 exposing the first polymer to hydrogen sulfide. 
 
     
     
       3. The method of  claim 1 , further comprising:
 exposing the first polymer to a thiol compound. 
 
     
     
       4. The method of  claim 1 , wherein the first monomer is one of an amino-substituted styrene, an amino-substituted bisphenol, an amino-substituted aromatic diol, and an amino-substituted methacrylate. 
     
     
       5. The method of  claim 1 , wherein polymerizing the second monomer and forming the first polymer includes a radical initiated polymerization. 
     
     
       6. The method of  claim 1 , wherein the first primary amine compound has the same chemical structure as the first monomer. 
     
     
       7. The method of  claim 1 , wherein the 1,3,5-hexahydrotriazine group is pendant on the first polymer. 
     
     
       8. The method of  claim 1 , wherein the 1,3,5-hexahydrotriazine group is part of a crosslink in the first polymer. 
     
     
       9. The method of  claim 1 , wherein the first polymer is a copolymer of the second monomer and a third monomer. 
     
     
       10. The method of  claim 9 , wherein the third monomer is styrene. 
     
     
       11. The method of  claim 1 , further comprising:
 exposing the first polymer to acid and forming a second polymer including a primary amine functional group. 
 
     
     
       12. A method, comprising:
 polymerizing a first monomer including a primary amine functional group and forming a first polymer including the primary amine functional group; and 
 exposing the first polymer to paraformaldehyde and a first primary amine compound and forming a second polymer including a 1,3,5-hexahydrotriazine group. 
 
     
     
       13. The method of  claim 12 , wherein the first primary amine compound has the same chemical structure as the first polymer. 
     
     
       14. The method of  claim 12 , further comprising:
 exposing the second polymer to hydrogen sulfide or a thiol compound. 
 
     
     
       15. The method of  claim 12 , wherein the first monomer is one of an amino-substituted styrene, an amino-substituted bisphenol, an amino-substituted aromatic diol, and an amino-substituted methacrylate. 
     
     
       16. The method of  claim 12 , wherein the first polymer is one of a block copolymer, a star polymer, a comb polymer, and a hyperbranched polymer. 
     
     
       17. The method of  claim 12 , further comprising:
 exposing the second polymer to acid and re-forming the first polymer.